Water-containing detergent mixtures comprising oligoglycoside surfactants

ABSTRACT

An aqueous detergent composition containing: (a) from 12 to 15% by weight of a nonionic surfactant selected from the group consisting of alkyl oligoglycosides, alkenyl oligoglycosides, and mixtures thereof; (b) from 20 to 30% by weight of an alkyl sulfate; (c) from 40 to 60% by weight of an alkyl ether sulfate, and (d) from 12 to 15% by weight of a component selected from the group consisting of amphoteric surfactants, zwitterionic surfactants, and mixtures thereof, all weights being based on the solids content of the composition.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to water-containing detergent mixtures comprisingalkyl and/or alkenyl oligoglycosides, alkyl sulfates, alkyl ethersulfates and amphoteric or zwitterionic surfactants, to manualdishwashing detergents containing these mixtures and to the use of themixtures for the production of surface-active preparations.

2. Discussion of Related Art

Alkyl oligoglycosides and, in particular, alkyl oligoglucosides arenonionic surfactants which, by virtue of their native raw material base(fatty alcohol and sugar), are acquiring increasing significance and areused, for example, in manual dishwashing detergents or cosmetic products[cf. Tens. Surf. Det. 28, 413 (1991)]. However, despite good performanceresults, there is still a need for detergent mixtures based on alkylglucosides of which the performance level synergistically exceeds thatof the individual components.

There has hitherto been no shortage of attempts to develop detergentmixtures based on alkyl oligoglucosides which have advantageousproperties.

EP-B-0 070 074, EP-B-0 070 075, EP-B-0 070 076 and EP-B-0 070 077(Procter & Gamble), for example, describe high-foaming combinations ofalkyl oligoglucosides with anionic surfactants, such as soaps,alkylbenzene sulfonates, fatty alcohol sulfates, conventional fattyalcohol ether sulfates, α-olefin sulfonates and alkane sulfonates and,optionally, betaine surfactants.

DE-A1 35 34 082 describes skin-friendly dishwashing detergentscontaining a combination of anionic sulfate or sulfonate surfactants,alkyl oligoglucosides and fatty acid alkanolamides.

However, where these known detergent mixtures are used in surface-activepreparations, reductions in performance and ecotoxicologicalcompatibility have hitherto had to be accepted in some cases.

Accordingly, the problem addressed by the present invention was todevelop detergent mixtures based on alkyl and/or alkenyl oligoglycosideshaving further improved properties.

DESCRIPTION OF THE INVENTION

The present invention relates to water-containing detergent mixturescomprising--based on the solids content--

a) 5 to 20% by weight of alkyl and/or alkenyl oligoglycosides,

b) 25 to 40% by weight of alkyl sulfates,

c) 35 to 65% by weight of alkyl ether sulfates and

d) 5 to 20% by weight of amphoteric or zwitterionic surfactants.

It has surprisingly been found that the detergent mixtures according tothe invention have a washing, dishwashing, foaming and cleaning powerand a skin-cosmetic compatibility which exceed those of the individualcomponents through synergistic enhancement.

a) Alkyl and/or alkenyl oligoglycosides (APG) are known substances whichmay be obtained by the relevant methods of preparative organicchemistry. EP-A1-0 301 298 and WO 90/3977 are cited as representative ofthe extensive literature available on the subject.

The alkyl and/or alkenyl oligoglycosides correspond to formula (I)

    R.sup.1 --O--[G].sub.p                                     (I)

in which R¹ is a linear or branched alkyl or alkenyl radical containing4 to 22 carbon atoms, [G] is a glycose unit containing 5 or 6 carbonatoms and p is a number of 1 to 10.

The alkyl and/or alkenyl oligoglycosides may be derived from aldoses orketoses containing 5 or 6 carbon atoms, preferably from glucose.Accordingly, the preferred alkyl and/or alkenyl oligoglycosides arealkyl and/or alkenyl oligoglucosides.

The index p in general formula (I) indicates the degree ofoligomerization (DP degree), i.e. the distribution of mono- andoligoglycosides, and is a number of 1 to 10. Whereas p in a givencompound must always be an integer and, above all, may assume a value of1 to 6, the value p for a certain alkyl oligoglycoside is ananalytically determined calculated quantity which is generally a brokennumber. Alkyl and/or alkenyl oligoglycosides having an average degree ofoligomerization p of 1.1 to 3.0 are preferably used. Alkyl and/oralkenyl oligoglycosides having a degree of oligomerization below 1.7and, more particularly, between 1.2 and 1.4 are preferred from theperformance point of view.

The alkyl or alkenyl radical R¹ may be derived from primary alcoholscontaining 4 to 11 and preferably 8 to 10 carbon atoms. Typical examplesare butanol, caproic alcohol, caprylic alcohol, capric alcohol andundecyl alcohol and technical mixtures thereof such as are obtained, forexample, in the hydrogenation of technical fatty acid ethyl esters or inthe hydrogenation of aldehydes from Roelen's oxo synthesis. Alkyloligoglucosides having a chain length of C₈ to C₁₀ (DP=1 to 3), whichare obtained as first runnings in the separation of technical C₈₋₁₈coconut oil fatty alcohol by distillation and which may contain lessthan 6% by weight C₁₂ alcohol as an impurity, and alkyl oligoglucosidesbased on technical C_(9/11) oxoalcohols (DP=1 to 3) are preferred.

The alkyl or alkenyl radical R¹ may also be derived from primaryalcohols containing 12 to 22 and preferably 12 to 14 carbon atoms.Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol,palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleylalcohol, behenyl alcohol, erucyl alcohol and technical mixtures thereofwhich may be obtained as described above. Alkyl oligoglucosides based onhydrogenated C_(12/14) coconut oil alcohol having a DP of 1 to 3 arepreferred.

b) Fatty alcohol sulfates (FAS) which may be used in accordance with theinvention correspond to formula (II)

    R.sup.3 O--SO.sub.3 X                                      (II)

in which R³ is a linear or branched alkyl or alkenyl radical containing6 to 22 carbon atoms and X is an alkali metal or alkaline earth metal.

These substances are also known chemical compounds which may be obtainedby sulfation of fatty alcohols. Typical examples are the sulfates ofcaproic alcohol, caprylic alcohol, capric alcohol, lauryl alcohol,myristyl alcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol,oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol and erucyl alcohol and technicalmixtures thereof. Sulfates of technical C_(12/18) coconut oil fattyalcohol or C_(16/18) tallow fatty alcohol cuts in the form of theirsodium salts are preferably used.

c) Fatty alcohol ether sulfates (FES), which may be used in accordancewith the invention, correspond to formula (III)

    R.sup.3 O--(CH.sub.2 CH.sub.2 O).sub.n --SO.sub.3 X        (III)

in which R³ is a linear or branched alkyl or alkenyl radical containing6 to 22 carbon atoms, n is a number of 1 to 10 and X is an alkali metalor alkaline earth metal.

These substances are also known chemical compounds which may obtained bysulfation of fatty alcohol polyglycol ethers. It is preferred to use FESof the NRE type (NRE=narrow range ethoxylates) which are described, forexample, in International patent application WO 91/05 764 and in thesynoptic Article by D. L. Smith in J. Am. Oil. Chem. Soc. 68, 629(1991).

Typical examples are the sulfation products of adducts of 1 to 10 molesof ethylene oxide (normal-range or narrow-range) with 1 mole of caproicalcohol, caprylic alcohol, capric alcohol, lauryl alcohol, myristylalcohol, cetyl alcohol, palmitoleyl alcohol, stearyl alcohol, oleylalcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol,gadoleyl alcohol, behenyl alcohol and erucyl alcohol and also technicalmixtures thereof. Sulfates of adducts of 2 to 7 moles of ethylene oxidewith saturated coconut oil fatty alcohols containing 12 to 18 carbonatoms in the form of their sodium, potassium and/or magnesium salts arepreferred. It is preferable to use fatty alcohol ether sulfates derivedfrom corresponding fatty alcohol polyglycol ethers which, in turn, havebeen produced in the presence of calcined or, more particularly,hydrophobicized hydrotalcite and which therefore have a particularlyadvantageous narrow homolog distribution.

d) Suitable amphoteric or zwitterionic surfactants are, for example,alkyl betaines, alkyl amidobetaines, aminopropionates, aminoglycinates,imidazolinium betaines and/or sulfobetaines.

Typical examples are the reaction products of primary or tertiary fattyamines, fatty acid amides, fatty acid aminoamines or fatty alkylimidazolines with sodium chloroacetate, acrylates orchlorohydroxypropane sulfonic acid. Information on the production andstructure of the compounds mentioned can be found in Falbe (ed.),"Surfactants in Consumer Products", Springer-Verlag, 1986, pages114-119. Alkylamidobetaines obtained by condensation of technicalC_(12/14) or C_(12/18) coconut oil fatty acid with dimethylaminopropylamine and subsequent reaction with sodium chloroacetate are preferred.

Water-containing detergent mixtures distinguished by particularlyadvantageous performance properties comprise--based on the solidscontent

a) 12 to 15% by weight of alkyl and/or alkenyl oligoglycosides,

b) 20 to 30% by weight of alkyl sulfates,

c) 40 to 60% by weight of alkyl ether sulfates and

d) 12 to 15% by weight of amphoteric or zwitterionic surfactants.

In addition, the following components have proved to be particularlyadvantageous (within the predetermined limits):

fatty alcohol sulfates and fatty alcohol ether sulfates in a ratio byweight of 66:34,

the alkyl and/or alkenyl oligoglycosides and the amphoteric orzwitterionic surfactants in a ratio by weight of 50:50 and

the fatty alcohol sulfates/fatty alcohol ether sulfates on the one handand the alkyl and/or alkenyl oligoglycosides/amphoteric or zwitterionicsurfactants on the other hand in a ratio by weight of 70:30.

In gauging the ratio by weight of fatty alcohol sulfate to fatty alcoholether sulfate, it is important to take into account the fact that FESstill generally contain fractions of corresponding FAS.

The water-containing detergent mixtures may be produced by simplemechanical mixing of aqueous solutions of the components, optionally atelevated temperatures of 30° to 50° C.; no chemical reaction takes placeduring the mixing process. The solids content of the water-containingdetergent mixtures may be between 15 and 50% by weight and is preferablybetween 20 and 40% by weight.

The present invention also relates to manual dishwashing detergentscontaining--based on the solids content

a) 5 to 20% by weight of alkyl and/or alkenyl oligoglycosides,

b) 25 to 40% by weight of alkyl sulfates,

c) 35 to 65% by weight of alkyl ether sulfates and

d) 5 to 20% by weight of amphoteric or zwitterionic surfactants.

In addition to the detergent mixtures mentioned, the water-based manualdishwashing detergents according to the invention may contain othertypical constituents, for example other anionic, nonionic or amphotericor zwitterionic co-surfactants, foam boosters, fragrances, etc. Atypical formulation may contain, for example, 47% by weight of FES, 23%by weight of FAS, 15% by weight of APG and 15% by weight ofalkylamidobetaine, based on the solids content of the detergent. Thesolids content of the manual dishwashing detergents may be from 15 to50% by weight and is preferably from 20 to 40% by weight.

Industrial Applications

The detergent mixtures according to the invention are distinguished byexcellent washing, dishwashing and cleaning performance and byadvantageous skin-cosmetic and ecotoxicological compatibility.

Accordingly, the present invention also relates to their use in theproduction of laundry detergents, dishwashing detergents and cleaningpreparations, hair-care and personal hygiene preparations, in which theymay be present in quantities of 1 to 50% by weight and preferably inquantities of 10 to 30% by weight, based on the preparation.

The following Examples are intended to illustrate the invention withoutlimiting it in any way.

EXAMPLES I. Surfactants Used

APG: C_(12/14) coconut oil alkyl oligoglucoside Plantaren® APG 600 (30%by weight aqueous paste)

FAS: C_(12/14) coconut oil fatty alcohol sulfate Texapon® LS 35 (35% byweight aqueous paste)

FES: C_(12/14) coconut oil fatty alcohol 2EO adduct sulfate Na saltTexapon® NSO (28% by weight aqueous solution)

AMP: Betaine surfactant based on C_(12/14) coconut oil fatty acid amideDehyton® K

All the surfactants used are products of Henkel KGaA, Dusseldorf,Federal Republic of Germany.

II. Evaluation of Dishwashing Performance (DWP)

Dishwashing performance was determined by the saucer test [Fette,Seifen, Anstrichmitt., 74, 163 (1972)]. To this end, saucers 14 cm indiameter were each soiled with 2 cm³ beef tallow (acid value 9-10) andstored for 24 h at room temperature. The saucers were then rinsed at 50°C. with 5 liters of tap water having a hardness of 16° d. The testmixture was used in a dosage of 0.15 g of active substance/1. Thedishwashing test was terminated when the foam had completelydisappeared. The results of the dishwashing tests, expressed as thenumber of clean saucers, are set out in Table 1:

                  TABLE 1                                                         ______________________________________                                        Performance tests                                                             Percentages in % by weight                                                           APG       FAS    FES     AMP   DWP                                     Ex.    %         %      %       %     %                                       ______________________________________                                        1      5         30     60      5     13.5                                    2      10        27     53      10    15                                      3      15        23     47      15    16                                      4      20        20     40      20    13.5                                    Cl     0         34     66      0     10.5                                    ______________________________________                                    

We claim:
 1. An aqueous detergent composition comprising:(a) from 12 to15% by weight of a nonionic surfactant selected from the groupconsisting of alkyl oligoglycosides, alkenyl oligoglycosides, andmixtures thereof; (b) from 20 to 30% by weight of an alkyl sulfate; (c)from 40 to 60% by weight of an alkyl ether sulfate, and (d) from 12 to15% by weight of a component selected from the group consisting ofamphoteric surfactants, zwitterionic surfactants, and mixtures thereof,all weights being based on the solids content of the composition.
 2. Thecomposition of claim 1 wherein said alkyl oligoglycosides and alkenyloligoglycosides correspond to formula I:

    R.sup.1 --O--(G).sub.p                                     (I)

wherein R¹ is a linear or branched alkyl or alkenyl radical containing 4to 22 carbon atoms, (G) is a glycose unit containing 5 or 6 carbonatoms, and p is a number from 1 to
 10. 3. The composition of claim 1wherein said alkyl sulfate corresponds to formula II:

    R.sup.3 O--SO.sub.3 X                                      (II)

wherein R³ is a linear or branched alkyl or alkenyl radical containing 6to 22 carbon atoms and X is an alkali metal or alkaline earth metal. 4.The composition of claim 1 wherein said alkyl ether sulfate correspondsto formula III:

    R.sup.3 O--(CH.sub.2 CH.sub.2 O).sub.n --SO.sub.3 X        (III)

wherein R³ is a linear or branched alkyl or alkenyl radical containing 6to 22 carbon atoms, n is a number from 1 to 10 and X is an alkali metalor alkaline earth metal.
 5. The composition of claim 1 wherein saidamphoteric and zwitterionic surfactants are selected from the groupconsisting of alkyl betaines, alkyl amidobetaines, aminopropionates,aminoglycinates, imidazolinium betaines, sulfobetaines, and mixturesthereof.
 6. The composition of claim 1 having a solids content of from15 to 50% by weight.
 7. The composition of claim 1 wherein saidcomponent (b) and said component (c) are present in said composition ina ratio by weight of 66:34, respectively.
 8. The composition of claim 1wherein said component (a) and said component (d) are present in saidcomposition in a ratio by weight of 50: 50, respectively.
 9. Thecomposition of claim 1 wherein said components (b)+(c) and saidcomponents (a)+(d) are present in said composition in a ratio by weightof 70:30, respectively.
 10. The process of claim 8 wherein said alkylsulfate corresponds to formula II:

    R.sup.3 O--SO.sub.3 X                                      (II)

wherein R³ is a linear or branched alkyl or alkenyl radical containing 6to 22 carbon atoms and X is an alkali metal or alkaline earth metal. 11.A process for producing an aqueous detergent composition comprisingcombining:(a) from 12 to 15% by weight of an aqueous nonionic surfactantselected from the group consisting of alkyl oligoglycosides, alkenyloligoglycosides, and mixtures thereof; (b) from 20 to 30% by weight ofan aqueous alkyl sulfate; (c) from 40 to 60% by weight of an aqueousalkyl ether sulfate, and (d) from 12 to 15% by weight of an aqueouscomponent selected from the group consisting of amphoteric surfactants,zwitterionic surfactants, and mixtures thereof, all weights being basedon the solids content of the composition.
 12. The process of claim 11wherein said alkyl oligoglycosides and alkenyl oligoglycosidescorrespond to formula I:

    R.sup.1 --O--(G).sub.p                                     (I)

wherein R¹ is a linear or branched alkyl or alkenyl radical containing 4to 22 carbon atoms, (G) is a glycose unit containing 5 or 6 carbonatoms, and p is a number from 1 to
 10. 13. The process of claim 8wherein said alkyl sulfate corresponds to formula II:

    R.sup.3 2O--SO.sub.3 X                                     (II)

wherein R³ id a linear or branched alkyl or alkenyl radical containing 6to 22 carbon atoms and X is an alkali metal or alkaline earth metal. 14.The process of claim 11 wherein said alkyl ether sulfate corresponds toformula III:

    R.sup.3 O--(CH.sub.2 CH.sub.2 O).sub.n --SO.sub.3 X        (III)

wherein R³ is a linear or branched alkyl or alkenyl radical containing 6to 22 carbon atoms, n is a number from 1 to 10 and X is an alkali metalor alkaline earth metal.
 15. The process of claim 11 wherein saidamphoteric and zwitterionic surfactants are selected from the groupconsisting of alkyl betaines, alkyl amidobetaines, aminopropionates,aminoglycinates, imidazolinium betaines, sulfobetaines, and mixturesthereof.
 16. The process of claim 11 wherein said composition has asolids content of from 15 to 50% by weight.
 17. The process of claim 11wherein said component (b) and said component (c) are present in saidcomposition in a ratio by weight of 66:34, respectively.
 18. The processof claim 11 wherein said component (a) and said component (d) arepresent in said composition in a ratio by weight of 50:50, respectively.19. The process of claim 11 wherein said components (b)+(c) and saidcomponents (a)+(d) are present in said composition in a ratio by weightof 70:30, respectively.
 20. The process of claim 11 wherein saidcomposition contains an auxilliary component selected from the groupconsisting of anionic co-surfactants, nonionic co-surfactants,amphoteric co-surfactants, zwitterionic co-surfactants, foam boosters,fragrances, and mixtures thereof.